Preparation of unsaturated fluorochlorocarbon



Patented Feb. 23, 1954 PREPARATION OF UNSATURATED FLUORO- CHLORJOCARBON Charles B. Miller, Lynbrook, N. Y., and John D.

Calfee, Dayton,

Ohio, assignors to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 3, 1951, Serial N0. 240,286

2 Claims.

' This invention relates to the preparation of chlorofluoro derivatives of aliphatic hydrocarbons, particularly to the preparation of CC12=CC1F, a material useful as a chemical intermediate.

According to prior art procedures for the preparation of CC12=CC1F, it has been the practice to treat CClsCClzF with zinc in the presence of methyl alcohol according to the following reaction:

inexpensive process giving good yield of soughtfor material.

' We have now discovered that when CCl2=CCl2, a readily available and inexpensive raw material, is treated i. e., fluorinated, in the gas phase with gaseous HF in the presence of aluminum fluoride catalyst at certain temperatures, a chlorine atom of the CC12=CC12 is replaced by fluorine resulting in the formation of CclzzCClF. Aluminum fluoride catalysthas the property of promoting. the fluorination of CCl2=CCl2 to form CC12=CC1F under readily maintained operating conditions to such an extent that when CC12=CC12 is contacted in the presence of HF with suitable aluminum fluoride catalyst, fluorination to CClzzCClF takes place with good yields (percentage of the sought-for material recovered based on the amount of such material theoretically obtainable from the CClz:CClz converted) and conversions (amount of CCl2=CC12 which undergoes reaction) to desired products as compared with previouslyproposed procedures.

A variety of types of aluminum fluoride is known in the art. Such materials consist of lumps or smaller discrete particles, which lumps or particles in turn are composed of AlFa crystals of relatively large size, i. e. not less than about 1000 and usually several thousand Angstrom units radius and above, as in the case of commercial types of aluminum fluoride available on the market. According to the preferredform of our invention, substantially anhydrous aluminum aluminum fluorides which contain at least about;

95% A1F3, preferably at-least about 98% "AlFs,

ordinarily possess the desired catalytic activity. Raw commercial aluminum fluorides may contain certain amounts of water, e. g. water of hydration. In order to produce the anhydrous aluminum fluoride catalyst desired for the purpose of the present invention, such water is removed by heating under conditions to completely dry the aluminum fluoride while preventing hydrolysis thereof, e. g. heating atabout 450 C. until the bulk of the water is removed and thereafter further heating at above about 600 C. until residual amounts of water have been removed.

Certain forms of aluminum fluoride when examined even under the highest powered microscope, appear to be of non-crystalline or amorphous structure. When such amorphous aluminum fluorides are examined using X-ray diifraction technique, extremely small sub-microscopic crystals, i. e. crystallites, which have crystal size of below about 1000 A. radius may be detected. According to an alternative embodiment of our invention, such amorphous and substantially anhydrous aluminum fluorides having crystals below about 1000 A. radius are used in the fluorination of CC12=CC12 to CC12=CCIF. Within this embodiment of the invention particular aluminum fluoride catalysts are those composed of crystallites having radius below about 500 A, preferably below about 200 through the tube for 5 hours while maintaining internal tube temperature not above about C. During the latter 5 hour treatment, as reaction intensity gradually decreased, the percentage of nitrogen in the gas stream was also decreased. The temperature of the reactor was thereupon slowly raised to 300C. while continuing'passage of a slow- HF stream (in the absence of nitrogen) through the tube for an additional period of 2 hours. At this point, the reactor efiluent gas contained only HF and was substantially free of HCl. 88 parts of aluminum fluoride containing 98% AlFs and less than 0.15% chlorine, in hard granular form and having substantially the same mesh size, as the aluminum chloride, were. .re-, 7 covered. An X-ray diiiraction pattern of material prepared according to the method outlined above was made, which indicated crystallite size to be less than 200 A radius, i. e. the crystallite size was so small as to be indicative of amorphous structure.

If desired, in fluorinating CC12:CC12 the catalyst may be used in the form of a fluidized solid bed or suspended on a non-siliceous inert carrier such as activated alumina, activated car bon, metal fluorides or nickel.

While the mechanism of the reaction of this invention is not entirely clear, the over-all efiect appears to be that the fluorine ofthe HF replaces the chlorine of the CClz CClz according to the following reaction:

Reaction zone temperatures are maintained at or above the level at which all materials introduced into the reaction are completely in the gas phase and also at or above the level at which fiuorination of CClz=CClz in the presence of HF begins to take place. The broad range of temperatures suitable for producing fluorination' of CCl2=CCl2 is approximately 500-750 C. When either the crystalline AlFa (greater than about 1000 A. radius) or the non -crystalline AlFs (smaller than 1000 A. radius) is employed, no particular advantage accrues when temperatures are maintained above about 750 C. and temperatures reaction zone is dependent upon variables such as scale of operation, quantity of catalyst in the reactor and the specific operation employed, and may be best determined by a test run.

1 The molar ratio of HP to CCl2=CClz is maintained sufficiently high to supply the amount of fluorine required to bring about the desired fluorination of CCl2=CCl2 to form CCl2=CClF. Fluorination to an appreciable extent may be noted at molar ratios of HF to CC12=CC12 as low above this level are ordinarily avoided to prevent possible decomposition of reactants and/or products and to avoid other possible inherent economic disadvantages. When, the preferred crystalline form of catalyst is used (containing crystallites of about 1000 A. radius and above) fluorination begins to occur at an appreciable rate at temperature of about 600 C. and hence temperatures in the approximate range of 600- 750 C., preferably 650- 700 C. are maintained when utilizing crystalline aluminum fluoride.

If lower fiuorination temperatures are desired, non-crystalline aluminum fluoride catalyst is utilized since it has been found that such catalyst promotes desired fluorination at temperatures as low as 500 C. Hence, temperatures in the approximate range of 500-600" C. are feasible when utilizing the latter type of catalyst. Aluminum fluorides composed of crystallites of size below about 500 A. radius, preferably below about 200 Aradius, are more adept at promoting fluorine.- tion within the 500600C. range than are cata lysts having largercrystallites. However, elevated temperatures tend to promote crystallite to crystal growth and thereby cause transformation of non-crystalline aluminum fluoride'into crystalline aluminum fluoride'and hence; par ticularly when maintaining temperature approaching the 600 C. level, it may be found that the original non-crystalline fluoride is gradually converted into aluminum fluoride having larger crystallites and even into aluminum fluoride hav ing crystals greater than about 1000 A. radius, thereby requiring a gradual upward shift influorination temperature.

The time of contact of CC12=CClz wi.th t e aluminum fluoride catalyst may be varied to some extent without noticeable sacrifice in yield andefliciency of operation. However, if contact time is excessive, i. e. very low space velocities, the capacity of the reactor is low, thereby causing economic disadvantages in the operation. On the other hand, if contact time is too short, i. e. at excessively high space velocities, the fluorination of CCl2=CClz to form the desired product maybe as about /2:1 but ratios of about 1:1 or above should beused for more complete fluorination. Preferably ratios substantially in excess of 111 are employed, since mass action favors formation of desired product when excess quantities of HF are present. Maximum ratios are limited only by desired high reactor capacity, i. e. excessively high ratios tend to produce high gas velocities and consequent short time of contact between reactant and catalyst and incompleteness of fluorination, thereby necessitating lower space velocity and consequent lower reactor output.

For convenience, atmospheric pressure opera-, tion is preferred. The reaction may, if desired, be carried out at super-atmospheric or sub-atmospheric pressure, the choice being largely one of convenience, e. g. determined by the nature of prior treatment of the starting material or' subsequent treatment of the reaction product.

Generally, the process of the invention is carried out by contacting the CCls=CC12 with an aluminum fluoride catalyst described above in the presence of gaseous HF at temperature at which the fluorination takes place. Operations may be suitably carried out by introducing the gaseous material comprising (3012:0012 into a reaction zone contain ng aluminum fluoride having the L properties set forth above and heating said material in the zone at temperatures heretofore iii-- dicated for a time sufiicient to convert an appreciable amount of CClz CClz to CClzzCClF, withdrawing gaseous products fromthe zone and recovering said CCI2 CC1F from the gaseous products. Although not limited to continuous operations, the process of ourinvention may be, advantageously carried out thereby. It-is preferable toutilize pure CC12=CC12 as starting -inateri-al and introduce such material in the gas phase mixedwith HF into the reaction zone; However, this does not preclude. introducing; CClz=CClz diluted with other's us a r al. e. g. an inert gas such as nitrogen, into the reaction zone. If such impure CCl2==CCl2 is 'avail-. able and it is desirable to carry out fiuorination thereof to produce the above indicated products, this material may be'introduced into the reaction zone, contacted with aluminum fluoride catalyst in the presence of gaseous HF and fiuorination of the CClz CClz thereby brought about to produce Various reaction products in the reaction zonev exit gas stream may be recovered separately or in- Suitably,

admixture in any suitable manner. the gas discharged from the reactor is recovered byv scrubbing with water to remove HCl and HF through a condenser cooled to about minus 78 0. with solid carbon dioxide and acetone mixture to condense any extremely low boiling material present. The principal products condensed are 0012:0015 (boiling point plus 71 0.) and 0012:0012 (boiling point plus 121 0.), and in addition trace amounts of CClFa (boiling point minus 83C.) and 001F20F3 (boiling point minus 3801). Individual compounds may be recovered, e. g. by distillation, from condensates obtained above. Any unreacted 0012:0012 may be recycled to subsequent operation.

Any suitable chamber or reactor tube constructed of inert material may be employed for carrying out the reaction provided the reaction zone afforded is of sufiicient length and crosssectional area to accommodate the required amount of aluminum fluoride necessary to provide adequate gas contact area, and at the same time afford sufficient free space for passage of the gas mixture at an economical rate of flow. Material such as nickel, graphite, inconel and other materials resistant to HF may be mentioned as suitable for use as reactor tube. Externally disposed reactor tube heating means such as electrical resistance heaters may be supplied.

The following examples illustrate the practice of our invention, parts and percentages being by weight:

Example 1.100 parts of substantially anhydrous aluminum fluoride catalyst having crystallite size less than 500 A. radius prepared by reacting anhydrous aluminum fluoride with gaseous anhydrous HF were arranged in a fixed bed supported on a nickel screen in a vertically mounted /4 internal diameter, 3-foot long nickel tube. The tube was externally electrically heated and the tube ends were fitted with pipe connections for the inlet and outlet of a gas stream and for the insertion into the nickel tube and catalyst bed of a suitable thermocouple. A gaseous mixture of about 52 parts per hour of 0012:0012, and HF in ratio of about 1 mol of the former to 3 mols of the latter, was introduced into the bottom of the nickel tube and passed upwardly through the bed of AlFa. By suitably adjusting the electrical heaters thereby to control the rate of heat input into the gas stream, temperature of the catalyst bed was maintained at about 600 C. Gaseous products of the reaction were withdrawn overhead, cooled, thence passed successively through a water scrubber, a drier containing a0l2 as the drying agent and a condenser held at about minus 78 0. by means of an external cooling bath of carbon dioxide ice and acetone. Products were identified by boiling point and infra-red spectrogram. Fractions boiling at minus to minus 0. (001F3), minus 45 0. (0Ft00l2F), a principal fraction boiling at plus 72 0., identified as 0012:0011, and unreacted HF and 0012:0012 were obtained. 0onversion of HF to fluorinated products was 36% and about 50% of the 0012:0012 charged was converted to 00l2:00lF.

Example 2.-A gaseous mixture of about 67 parts per hour of 0012:0012, and HF in ratio of about one mol of the former to about 3.5 mole of the latter was passed through the nickel tube and catalyst bed employed in Example 1, while maintaining catalyst bed temperature at 750 0. Gaseous products were withdrawn from the tube and treated and recovered as in Example 1. The foregoing operating conditions were maintained for 3 /2 hours, after which time the aluminum fluoride catalyst had become substantially completely crystalline (crystal size greater than about 1000 A. radius). In the succeeding 2 hours, during which time parts of 0012:0012 were passed through the tube, 15 parts of 0012:0011 were formed and subsequently recovered. 0onversion of HF to fluorinated products was 40%.

We claim:

1. The process for fiuorinating 0012:0012 which comprises contacting said 0012:0012 in the presence of sufficient gaseous HF to form 0012:0011 and at fluorination temperature in the approximate range 500-750 0. with aluminum fluoride catalyst, for time sufiicient to fluorinate an appreciable amount of said. 0012:0012 to form 0012:001F.

2. The process for fluorinating 0012:0012 to 00l2=00lF which comprises introducing a gaseous material comprising 0012:0012 and at least an equimolecular amount of gaseous HF mixed therewith into a reaction zone containing aluminum fluoride catalyst having crystal size at least as great as about 1000 Angstrom units radius, heating said material in said zone at temperature in the approximate range BSD-700 0. for time suilicient to fluorinate an appreciable amount of said 0012:0012 to form gaseous product comprising 0012:001F, withdrawing gaseous product from said zone, and recovering said 0012:0015 from said gaseous product.

CHARLES B. MILLER. JOHN D. CALFEE.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,996,115 Lazier Apr. 2, 1935 2,466,189 Waalkes Apr. 5, 1949 2,471,525 Hillyer et a1 May 31, 1949 

1. THE PROCESS FOR FLUORINATING CCL2=CCL2 WHICH COMPRISES CONTACTING SAID CCL2=CCL2 IN THE PRESENCE OF SUFFICIENT GASEOUS HF TO FORM CCL2=CCLF AND AT FLUORINATION TEMPERATURE IN THE APPROXIMATE RANGE 500-750* C. WITH ALUMINUM FLUORIDE CATALYST, FOR TIME SUFFICIENT TO FLUORINATE AN APPRECIABLE AMOUNT OF SAID CCL2=CCL2 TO FORM CCL2=CCLF. 